WO1999007779A1 - Matieres moulables en polycarbonate abs resistantes a la flamme et de stabilite dimensionnelle a la chaleur - Google Patents

Matieres moulables en polycarbonate abs resistantes a la flamme et de stabilite dimensionnelle a la chaleur Download PDF

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WO1999007779A1
WO1999007779A1 PCT/EP1998/004733 EP9804733W WO9907779A1 WO 1999007779 A1 WO1999007779 A1 WO 1999007779A1 EP 9804733 W EP9804733 W EP 9804733W WO 9907779 A1 WO9907779 A1 WO 9907779A1
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weight
molding compositions
parts
compositions according
formula
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PCT/EP1998/004733
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German (de)
English (en)
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Thomas Eckel
Dieter Wittmann
Michael Zobel
Heinrich Alberts
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Bayer Aktiengesellschaft
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Priority to AU91568/98A priority Critical patent/AU9156898A/en
Priority to KR1020007001368A priority patent/KR100554585B1/ko
Priority to JP2000506270A priority patent/JP4257688B2/ja
Priority to US09/485,284 priority patent/US6566428B1/en
Priority to EP98943796A priority patent/EP1003808B1/fr
Priority to CA002300218A priority patent/CA2300218C/fr
Priority to DE59804070T priority patent/DE59804070D1/de
Priority to BR9811887-0A priority patent/BR9811887A/pt
Priority to DK98943796T priority patent/DK1003808T3/da
Publication of WO1999007779A1 publication Critical patent/WO1999007779A1/fr
Priority to HK01101520A priority patent/HK1030619A1/xx

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C08L69/005—Polyester-carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene

Definitions

  • the present invention relates to polycarbonate ABS molding compositions which are flame-retardant with phosphorus compounds and which have an excellent level of mechanical properties, in particular a high heat resistance.
  • EP-A 0 640 655 describes molding compositions made from aromatic polycarbonate, styrene-containing copolymers and graft polymers which can be flame-retarded with monomeric and / or oligomeric phosphorus compounds.
  • EP-A-0363608 describes flame-retardant polymer mixtures made from aromatic polycarbonate, styrene-containing copolymer or graft copolymer and oligomeric phosphates as flame retardant additives. For some applications, such as molded parts in the interior of housing parts, the heat resistance of these mixtures is often not sufficient.
  • the object of the present invention is therefore to produce flame-retardant polycarbonate ABS molding compositions which have excellent heat resistance in addition to the required high flame-resistance.
  • the present invention therefore relates to flame-retardant thermoplastic molding compositions
  • Parts by weight of aromatic polycarbonate or polyester carbonate B) 1 to 60, preferably 1 to 40 parts by weight, particularly preferably 2 to 30 parts by weight, of at least one graft polymer of
  • thermoplastic vinyl (co) polymer 0 to 50, preferably 1 to 30, particularly preferably 2 to 25 parts by weight of thermoplastic vinyl (co) polymer
  • halogen preferably chlorine and / or bromine
  • C 1 -C 6 -alkyl preferably C 1 -C 6 -alkyl, in particular methyl, Cg-C 1 -Q aryl, preferably phenyl, C 1 -C 4 -aralkyl, preferably phenyl-C 1 -C 4 4 alkyl, especially benzyl, Rl, R ⁇ , R ⁇ and R ⁇ , independently of one another, optionally halogenated Cj-Cg-alkyl, in each case optionally C 5 -C6 -cycloalkyl, C6-C20-aryl or C7- substituted by halogen and / or Ci-C-alkyl Ci2-aralkyl,
  • y each independently of one another 0, 1, 2, 3 or 4,
  • n independently of one another 0 or 1, preferably 1,
  • N 0.3 to 30
  • X represents a mono- or polynuclear aromatic radical with 6 to 30 C atoms with the exception of diphenyl
  • Aromatic polycarbonates and / or aromatic polyester carbonates according to component A which are suitable according to the invention are known from the literature or can be prepared by processes known from the literature (for the production of aromatic polycarbonates see, for example, Schnell, “Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964, and DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396; for the production of aromatic polyester carbonates, for example DE-OS 3 077 934 ).
  • Aromatic polycarbonates are produced e.g. by reacting diphenols with carbonic acid halides, preferably phosgene and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalogenides, according to the phase interface method, if appropriate using chain terminators, for example monophenols and optionally using trifunctional or more than trifunctional branching agents, for example triphenols or tetraphenols.
  • Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (III)
  • AI is a single bond, Ci-Cs-alkyls, C2-C5-alkylidene, Cs-Cg-cycloalkylene, -O-, -SO-, -CO-, -S-, -SO2-, Cg-C ⁇ aryls , which with other optionally aromatic rings containing heteroatoms may be condensed, or a radical of the formula
  • Cj-Cg-alkyl preferably C r C 4 -alkyl, in particular methyl, halogen, preferably chlorine and / or bromine, Cg-Ci Q- aryl, preferably phenyl, C 7 -C 1 aralkyl, phenyl-C r C 4 alkyl, preferably benzyl,
  • R 5 and R 6 can be selected individually for each Z, independently of one another, hydrogen or C 1 -C 6 -alkyl, preferably hydrogen, methyl and / or ethyl,
  • n is an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom Z
  • R5 and R6 are simultaneously alkyl.
  • Preferred diphenols are hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis- (hydroxyphenyl) -C ⁇ -C5-alkanes, bis- (hydroxyphenyl) -C5-C6-cycloalkanes, bis- (hydroxyphenyl) ethers, bis - (Hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones and, ⁇ -bis (hydroxyphenyl) diisopropyl benzenes such as their core-brominated and / or core-chlorinated derivatives.
  • diphenols are 4,4'-diphenylphenol, bisphenol-A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis - (4-hydroxyphenyl) -3, 3, 5 -trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and their di- and tetrabrominated or chlorinated derivatives such as 2,2-bis- (3- Chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.
  • 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A) is particularly preferred.
  • the diphenols can be used individually or as any mixtures.
  • the diphenols are known from the literature or can be obtained by processes known from the literature.
  • Suitable chain terminators for the production of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or
  • 2,4,6-tribromophenol but also long-chain alkylphenols, such as 4- (1,3-tetramethylbutyl) phenol according to DE-OS 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3,5-dimethylheptyl) phenol and 4- (3rd , 5-dimethylheptyl) phenol.
  • Chain terminators are generally between 0.5 mol% and 10 mol%, based on the molar sum of the diphenols used in each case.
  • the thermoplastic, aromatic polycarbonates have average weight-average molecular weights (M w , measured, for example, by means of an ultracentrifuge or scattered light measurement) of 10,000 to 200,000, preferably 20,000 to 80,000.
  • thermoplastic, aromatic polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of> three-functional compounds, for example those with> three phenolic groups.
  • copolycarbonates Both homopolycarbonates and copolycarbonates are suitable.
  • component A 1 to 25% by weight, preferably 2.5 to 25% by weight (based on the total amount of diphenols to be used), polydiorganosiloxanes with hydroxy-aryloxy end groups can also be used. These are known (see, for example, from US Pat. No. 3,419,634) or can be produced by processes known from the literature.
  • the production of polydiorganosiloxane-containing copolycarbonates is e.g. in DE-OS 3 334 782.
  • preferred polycarbonates are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sum of diphenols, of other diphenols mentioned as preferred or particularly preferred, in particular of 2,2-bis (3 , 5-dibromo-4-hydroxyphenyl) propane.
  • Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid,
  • Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio between 1:20 and 20: 1 are particularly preferred.
  • a carbonic acid halide preferably phosgene, is additionally used as a bifunctional acid derivative in the production of polyester carbonates.
  • chain terminators for the production of the aromatic polyester carbonates in addition to the monophenols already mentioned, there are also their chlorocarbonic acid esters and the acid chlorides of aromatic monocarboxylic acids, which may optionally be substituted by C] -C22-alkyl groups or by halogen atoms, and aliphatic C2-C22-monocarboxylic acid chlorides.
  • the amount of chain terminators is in each case 0.1 to 10 mol%, based on moles of diphenols in the case of the phenolic chain terminators and on moles of dicarboxylic acid dichlorides in the case of monocarboxylic acid chloride chain terminators.
  • the aromatic polyester carbonates can also contain aromatic hydroxycarboxylic acids.
  • the aromatic polyester carbonates can be linear as well as known
  • 3- or polyfunctional carboxylic acid chlorides such as trimesic acid trichloride, cyanuric acid trichloride, 3,3'-4,4'-benzophenonetetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or
  • Pyromellitic acid tetrachloride in amounts of 0.01 to 1.0 mol% (based on the dicarboxylic acid dichlorides used) or 3- or polyfunctional phenols, such as phloroglucin, 4,6-dimethyl-2,4,6-tri- (4- hydroxyphenyl) -hepten-2,4,4-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1 -Tri- (4-hydroxyphenyl) ethane, tri- (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4 -Bis (4-hydroxyphenyl-isopropyl) phenol, tetra- (4-hydroxyphenyl) methane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2 -
  • the proportion of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups and carbonate groups.
  • Both the ester and the carbonate content of the aromatic polyester carbonates can be present in the form of blocks or randomly distributed in the polycondensate .
  • the relative solution viscosity ( ⁇ re ⁇ ) of the aromatic polyester carbonates is in the range 1.18 to 1.4, preferably 1.22 to 1.3 (measured on solutions of 0.5 g polyester carbonate in 100 ml methylene chloride solution at 25 ° C. ).
  • thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any mixture with one another.
  • Component B according to the invention is graft copolymers. These comprise graft copolymers with rubber-elastic properties which are essentially obtainable from at least 2 of the following monomers: chloroprene, 1,3-butadiene, isopropene, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and (meth) -Acrylic acid esters with 1 to 18 carbon atoms in the alcohol component; thus polymers as described, for example, in Methods of Organic Chemistry “(Houben-Weyl), Vol. 14/1, Georg Thieme-Verlag, Stuttgart 1961, pp. 393-406 and in CB Bucknall," Thoughened Plastics ", Appl. Science Publishers, London 1977.
  • Preferred polymers B are partially crosslinked and have gel contents of more than 20% by weight, preferably more than 40% by weight, in particular more than 60% by weight.
  • Preferred graft polymers B comprise graft polymers from:
  • Preferred graft polymers B are e.g. bases B.2 grafted with styrene and / or acrylonitrile and / or (meth) -acrylic acid alkyl esters such as polybutadienes. Butadiene styrene copolymers and acrylate rubbers; i.e. Copolymers of the
  • Particularly preferred graft polymers B are obtainable by grafting
  • ⁇ 10 to 70 preferably 15 to 50, in particular 20 to 40% by weight, based on graft polymate B, of at least one (meth) acrylic ester or 10 to 70, preferably 15 to 50, in particular 20 to 40% by weight of one Mixtures of 10 to 50, preferably 20 to 35% by weight, based on the mixture, acrylonitrile or (meth) -acrylic acid ester and 50 to 90, preferably 65 to 80% by weight, based on the mixture, styrene, as graft B. 1 on.
  • ⁇ 30 to 90 preferably 50 to 85, in particular 60 to 80% by weight, based on graft polymer B, of a butadiene polymer having at least 50% by weight, based on ⁇ , butadiene residues as the graft base B.2,
  • the gel fraction of the graft base ⁇ is at least 70% by weight (measured in toluene), the degree of graft G 0.15 to 0.55 and the average particle diameter d 50 of the graft polymer B.2 0.05 to 2 ⁇ m, preferably 0, Is 1 to 0.6 ⁇ m.
  • (Meth) -acrylic acid esters ⁇ are esters of acrylic acid or methacrylic acid with monohydric alcohols with 1 to 18 carbon atoms. Methyl methacrylate, ethyl ester and propyl ester, n-butyl acrylate, t-butyl acrylate and t-butyl methacrylate are particularly preferred.
  • the graft base ⁇ can contain up to 50% by weight, based on ⁇ , residues of other ethylenically unsaturated monomers, such as styrene, acrylonitrile, esters of
  • Acrylic or methacrylic acid with 1 to 4 carbon atoms in the alcohol component such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate), vinyl ester and / or vinyl ether.
  • the preferred graft base ⁇ consists of pure polybutadiene.
  • the degree of grafting G denotes the weight ratio of grafted graft monomers to the graft base and is dimensionless.
  • the average particle size d 50 is the diameter above and below which 50% by weight of the particles lie. It can be measured using an ultracentrifuge
  • Particularly preferred polymers B are e.g. also graft polymers
  • component B ⁇ . 10 to 80% by weight, based on component B, of at least one polymerizable, ethylenically unsaturated monomer as graft monomers C.1.
  • the acrylate rubbers ⁇ of the polymers B are preferably polymers of acrylic acid alkyl esters, optionally with up to 40% by weight, based on ⁇ , of other polymerizable, ethylenically unsaturated monomers.
  • the preferred polymerizable acrylic acid esters include C 1 -C 8 -alkyl esters, for example methyl,
  • Monomers with more than one polymerizable double bond can be copolymerized for crosslinking.
  • Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 C atoms and unsaturated monohydric alcohols with 3 to 12 C atoms or saturated polyols with 2 to 4 OH groups and 2 to 20 C atoms, such as ethylene glycol dimethacrylate, allyl - methacrylate; polyunsaturated heterocyclic compounds such as trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
  • Crosslinking monomers are preferably allyl methacrylate, ethylene glycol dimethyl acrylate, diallyl phthalate and heterocyclic compounds which have at least 3 ethylenically unsaturated groups.
  • crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, trivinyl cyanurate, triacryloylhexahydro-s-triazine and triallylbenzenes.
  • the amount of the crosslinking monomers is preferably 0.02 to 5, in particular 0.05 to 2,% by weight, based on the graft base ⁇ .
  • Preferred “other” polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, can optionally be used to prepare the graft base ⁇ , are, for example, acrylonitrile, styrene, ⁇ -methylstyrene, acrylamides, vinyl C 1 -C 6 -alkyl ether, methyl methacrylate, butadiene.
  • Preferred acrylate rubbers as the graft base ⁇ are emulsion polymers which have a gel content of at least 60% by weight.
  • graft bases according to B.2 are silicone rubbers with graft-active sites, as described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.
  • the gel content of the graft base B.2 is determined at 25 ° C. in dimethylformamide (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).
  • the graft polymers B can be prepared by known processes such as bulk, suspension, emulsion or bulk suspension processes.
  • the graft monomers are not necessarily grafted completely onto the graft base in the grafting reaction,
  • Graft polymers B also understood those products which are obtained by polymerizing the graft monomers in the presence of the graft base.
  • the average particle size d 50 is the diameter above and below which 50% by weight of the particles lie. It can be measured using an ultracentrifuge (W.
  • the graft monomers are not necessarily grafted completely onto the graft base in the grafting reaction,
  • Graft polymers B are also understood to mean those products which are obtained by (co) polymerizing the graft monomers in the presence of the graft base and are also obtained in the working up.
  • Component C comprises at least one thermoplastic vinyl (co) polymer.
  • Suitable as (co) polymers C are polymers of at least one monomer from the group of the vinyl aromatics, vinyl cyanides, such as unsaturated nitriles,
  • vinyl aromatics and / or nucleus-substituted vinyl aromatics such as, for example, styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene, and / or methacrylic acid (-CC) alkyl esters, such as methyl methacrylate, ethyl methacrylate, and
  • methyl cyanides such as unsaturated nitriles, for example acrylonitrile and methacrylonitrile and / or (meth) acrylic acid (-C-Cg) alkyl esters, e.g. Methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or unsaturated carboxylic acids, such as maleic acid and / or derivatives, such as anhydrides and imides of unsaturated carboxylic acids, such as maleic anhydride and N-phenyl-maleimide.
  • unsaturated nitriles for example acrylonitrile and methacrylonitrile and / or (meth) acrylic acid (-C-Cg) alkyl esters, e.g. Methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or unsaturated carboxylic acids, such as maleic acid and / or derivatives, such as an
  • the (co) polymers C are resinous, thermoplastic and rubber-free.
  • Copolymers of C. 1 styrene and C. 2 acrylonitrile are particularly preferred.
  • the (co) polymers according to C are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
  • the (co) polymers according to component C preferably have molecular weights M w (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000.
  • (Co) polymers according to component C frequently arise as by-products in the graft polymerization of component B, especially when large amounts of monomers B. 1 are grafted onto small amounts of rubber B.2.
  • the amount of C which may also be used according to the invention does not include these by-products of the graft polymerization of B.
  • the weight ratio of components B: C should be between 2: 1 and 1: 4, preferably between 1: 1 and 1: 2, in order to achieve the desired mechanical level for certain purposes .
  • the molding compositions according to the invention contain at least one phosphorus compound of the formula (I) as flame retardant
  • the radicals R 1 , R 2 , R3 ; R4 ⁇ A and n and y have the meaning given above.
  • the aromatic groups R 1 , R 2 , R3 ? R 4 and A can in turn be substituted with halogen and / or alkyl groups, preferably chlorine, bromine and / or C 1 -C alkyl.
  • Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.
  • N stands for values from 0.3 to 30, preferably for an average value of
  • N can assume the above-mentioned average values.
  • This mixture can contain monophosphorus compounds and / or oligomeric and / or polymeric phosphorus compounds.
  • N O, the formula (I) describes monophosphorus compounds.
  • Component D can be partially (at most up to 75% by weight) by at least one mono- and / or oligo- and / or poly-phosphorus compound of formula (II) which is different from compounds of formula (I) O
  • X in formula (II) represents a mono- or polynuclear aromatic radical having 6 to 30 carbon atoms with the exception of diphenyl.
  • Preferred residues are derived from diphenols according to formula (III) such as.
  • Monomeric and oligomeric phosphorus compounds of the formula (I) are preferably selected in the mixture so that a synergistic effect is achieved.
  • the mixture generally consists of 10 to 90% by weight of oligomeric and 90 to 10% by weight of monophosphorus compounds of the formula (I).
  • the monomeric phosphorus compounds and / or monophosphate compounds are preferably mixed with the complementary amount of oligomeric phosphate compounds in the range from 12 to 50, in particular from 14 to 40, very particularly preferably from 15 to 40% by weight.
  • Tributyl phosphate tris (2-chloroethyl) phosphate, tris (2,3-dibromopropyl) phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl 2-ethyl cresyl phosphate, tri- (isopropylphenyl) halophosphate substituted aryl phosphates, methylphosphonic acid dimethyl ester, methylphosphonic acid diphenyl ester, phenylphosphonic acid diethyl ester, triphenylphosphine oxide or tricresylphosphine oxide
  • the phosphorus compounds according to component D are generally known compounds of organic chemistry or can be prepared in an analogous manner by known methods (see, for example, Ullma ns Encyklopadie der Technische Chemie, vol. 18, pp. 301 ff 179, Houben-Weyl, methods of organic chemistry, Bd 12/1, S 43, Beistein, Bd 6, S 177)
  • the fluorinated polyolefins E are of high molecular weight and have glass transition temperatures of above -30 ° C., generally above 100 ° C., fluorine contents, preferably from 65 to 76, in particular from 70 to 76% by weight, average particle diameter d 50 of
  • the fluorinated polyolefins E have a density of 1.2 to 2.3 g cm 3.
  • Preferred fluorinated polyolefins E are polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene (hexafluoropropylene and Ethylene Tetrafluoroethylene Copolyme ⁇ sate
  • the fluorinated polyolefins are known (see "Vinyl and Related Polymers" by Schildknecht, John Wiley &
  • They can be prepared by known processes, for example by polymerizing tetrafluoroethylene in an aqueous medium with a free radical-forming catalyst, for example sodium, potassium or ammonium peroxydisulfate at pressures of 7 to 71 kg / cm 2 and at temperatures of 0 to 200 ° C, preferably at temperatures from 20 to 100 ° C (for more details see, e.g., US patent 2 393 967).
  • a free radical-forming catalyst for example sodium, potassium or ammonium peroxydisulfate
  • the density of these materials can be between 1.2 and 2.3 g / cm 3 , the average particle size between 0.5 and 1000 ⁇ m.
  • Fluorinated polyolefins E preferred according to the invention are tetrafluoroethylene polymers with average particle diameters of 0.05 to 20 ⁇ m, preferably 0.08 to
  • Suitable fluorinated polyolefins E that can be used in powder form are tetrafluoroethylene polymers with average particle diameters of 100 to 1000 ⁇ m and densities of 2.0 g / cm 3 to 2.3 g / cm 3 .
  • an aqueous emulsion (latex) of a graft polymer B is first mixed with a finely divided emulsion of a fluorinated polyolefin E;
  • Suitable emulsions of fluorinated polyolefins usually have solids contents of 30 to 70% by weight, in particular 50 to 60% by weight, preferably 30 to 35% by weight.
  • the quantity in the description of component B includes the proportion of
  • Graft polymer for the coagulated mixture of graft polymer and fluorinated polyolefins not.
  • the equilibrium ratio of graft polymer B to fluorinated polyolefin E in the emulsion mixture is 95: 5 to 60:40.
  • the emulsion mixture is coagulated in a known manner, for example by spray drying, freeze drying or coagulation by adding inorganic or organic salts, acids, bases or organic, water-miscible solvents, such as alcohols, ketones, preferably at temperatures of 20 to 150 ° C, in particular from 50 to 100 ° C. If necessary, drying can be carried out at 50 to 200 ° C., preferably 70 to 100 ° C.
  • Suitable tetrafluoroethylene polymer emulsions are commercially available products and are offered, for example, by DuPont as Teflon 30N.
  • the molding compositions according to the invention can contain at least one of the customary additives, such as lubricants and mold release agents, nucleating agents, antistatic agents, stabilizers and
  • Glass reinforcements optionally cut or ground, glass beads, glass balls, flake-like reinforcement materials, such as kaolin, talc, mica, mica, carbon fibers, are suitable as inorganic reinforcement materials. Cut or ground glass fibers are preferably used as the reinforcing material, preferably with a length of 1 to 10 mm and a diameter of ⁇ 20 ⁇ m in an amount of 1 to 40 parts by weight; the glass fibers are preferably surface-treated.
  • the molding compositions according to the invention can moreover have at least one polar compound of at least one of the metals of the 1st to 5th main group or the 1st to 8th
  • Subgroup of the periodic table with at least one element selected from the group of oxygen, sulfur, boron, carbon, phosphorus, nitrogen, hydrogen and silicon as finely divided inorganic powder.
  • an oxide or hydroxide preferably Ti0 2 , Si0 2 , Sn0 2 , ZnO, boehmite, Zr0 2 , A1 2 0 3 , iron oxides, their mixtures and doped compounds, particularly preferably boehmite or Ti0 2j with an average particle diameter of ⁇ 200 nm, preferably 0.1-100 nm, particularly preferably 1-50 nm.
  • the molding compositions according to the invention can contain one or more further, optionally synergistic flame retardants.
  • flame retardants are organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine formaldehyde resins, inorganic hydroxide compounds such as Mg, Al hydroxide, inorganic compounds such as antimony oxides, barium metaborate, hydroxoantimonate hydroxide, zirconium oxide, zirconium oxide, zirconium hydroxide, zirconium oxide Molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate and tin oxide as well as siloxane compounds.
  • These flame retardants are generally added in an amount of up to 20% by weight (based on the total molding composition).
  • the molding compositions according to the invention contain components A to E and, where appropriate, other known additives such as stabilizers, dyes, pigments,
  • Lubricants and mold release agents, nucleating agents, nanoparticles as well as antistatic agents and reinforcing materials and flame retardants are produced by mixing the respective components in a known manner and melt-compounding them in conventional units such as internal kneaders, extruders and double-shaft screws at temperatures of 200 ° C to 300 ° C and melt extruded, component E preferably being used in the form of the coagulated mixture already mentioned.
  • the individual constituents can be mixed in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at a higher temperature.
  • moldings of the present invention can be used for the production of moldings of any kind.
  • moldings can be produced by injection molding.
  • moldings that can be produced are: Housing parts of all types, eg. B. for household appliances such as juicers, coffee machines, mixers, for office machines such as monitors, printers, copiers or cover plates for the construction sector and parts for the motor vehicle sector. They are also used in the field of electrical engineering because they have very good electrical properties.
  • the molding compositions are particularly suitable for the production of molded parts, where particularly high demands are placed on the heat resistance of the plastics used.
  • Another form of processing is the production of molded articles by
  • Another object of the present invention is therefore also the use of the molding compositions according to the invention for the production of moldings of any kind, preferably those mentioned above, and the molding from the molding compositions according to the invention.
  • Graft polymer of 45 parts by weight of a copolymer of styrene and acrylonitrile in a weight ratio of 72:28 to 55 parts by weight of particulate crosslinked polybutadiene rubber (average particle diameter d5 Q 0.4 ⁇ m), produced by emulsion polymerization.
  • Fyrolflex RDP® from Akzo based on m-phenylene bis (diphenyl) phosphate.
  • Tetrafluoroethylene polymer as a coagulated mixture of a SAN graft polymer emulsion according to component C) in water and a tetrafluoroethylene polymer emulsion in water.
  • the weight ratio of graft polymer C) to tetrafluoroethylene polymer E) in the mixture is 90% by weight to 10% by weight.
  • Tetrafluoroethylene polymer emulsion has a solids content of 60% by weight, the average particle diameter is between 0.05 and 0.5 ⁇ m.
  • the SAN graft polymer emulsion has a solids content of 34% by weight and an average latex particle diameter of 0.4 ⁇ m.
  • the emulsion of the tetrafluoroethylene polymer (Teflon 30 N from DuPont) is mixed with the emulsion of the SAN graft polymer C and stabilized with 1.8% by weight, based on polymer solids, of phenolic antioxidants.
  • Teflon 30 N from DuPont
  • the emulsion of the tetrafluoroethylene polymer (Teflon 30 N from DuPont) is mixed with the emulsion of the SAN graft polymer C and stabilized with 1.8% by weight, based on polymer solids, of phenolic antioxidants.
  • MgSO- j Epsom salts
  • acetic acid at pH 4
  • Components A to E are mixed on a 3-1 kneader.
  • the moldings are produced on an Arburg 270 E injection molding machine at 260 ° C.
  • the notched impact strength is determined according to method ISO 180 1A on bars measuring 80 x 10 x 4 mm 3 at room temperature.
  • the heat resistance according to Vicat B is determined in accordance with DIN 53 460.
  • the stress crack behavior is investigated on bars measuring 80 x 10 x 4 mm 3 , melt temperature 260 ° C. A mixture of 60 vol . -% toluene and 40 vol .-% isopropanol used. The test specimens are pre-stretched using a circular template and 5 min or 10 min at room temperature in the
  • Test medium stored simultaneously.
  • the pre-stretch ⁇ x is 0.2 - 2.4%.
  • the stress crack behavior is assessed via the crack formation or the break depending on the pre-stretch.
  • the table shows that the molding compositions according to the invention show a very good combination of properties of the mechanical properties, in particular an improvement in the resistance to stress cracking, notched impact strength and the heat resistance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne des matières moulables thermoplastiques résistantes à la flamme et contenant: A. 5 à 95 parties en poids d'un polycarbonate ou polyestercarbonate aromatique; B. 1 à 60 parties en poids au moins d'un polymère greffé de B.1. 5 à 95 % en poids au moins d'un vinylmonomère sur B.2. 5 à 95 % en poids au moins d'une base de greffe à une température de transition vitreuse < 10 °C et avec une dimension moyenne de particules (valeur d50) de 0,05 à 5 νm; C. 0 à 50 parties en poids de vinylcopolymère thermoplastique; D. 0,5 à 20 parties en poids au moins d'un composé phosphoré de la formule générale (I) et éventuellement au moins un autre composé phosphoré différent des composés de la formule (I); E. 0,05 à 5 parties en poids d'une polyoléfine fluorée.
PCT/EP1998/004733 1997-08-11 1998-07-29 Matieres moulables en polycarbonate abs resistantes a la flamme et de stabilite dimensionnelle a la chaleur WO1999007779A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
AU91568/98A AU9156898A (en) 1997-08-11 1998-07-29 Flame-resistant thermostable polycarbonate abs moulding materials
KR1020007001368A KR100554585B1 (ko) 1997-08-11 1998-07-29 난연성의 내열성 폴리카르보네이트 ａｂｓ 성형 조성물
JP2000506270A JP4257688B2 (ja) 1997-08-11 1998-07-29 耐燃性、耐熱性ポリカーボネートａｂｓ成形材料
US09/485,284 US6566428B1 (en) 1997-08-11 1998-07-29 Flame-resistant thermostable polycarbonate ABS moulding materials
EP98943796A EP1003808B1 (fr) 1997-08-11 1998-07-29 Matieres moulables en polycarbonate abs resistantes a la flamme et de stabilite dimensionnelle a la chaleur
CA002300218A CA2300218C (fr) 1997-08-11 1998-07-29 Matieres moulables en polycarbonate abs resistantes a la flamme et de stabilite dimensionnelle a la chaleur
DE59804070T DE59804070D1 (de) 1997-08-11 1998-07-29 Flammwidrige wärmeformbeständige polycarbonat-abs-formmassen
BR9811887-0A BR9811887A (pt) 1997-08-11 1998-07-29 Massas de moldagem abs de policarbonato antichamas resistentes quanto à forma no calor
DK98943796T DK1003808T3 (da) 1997-08-11 1998-07-29 Flammeresistente termostabile polycarbonat-ABS-formmasser
HK01101520A HK1030619A1 (en) 1997-08-11 2001-03-01 Flame-resistant thermostable polycarbonate abs moulding materials.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19734663A DE19734663A1 (de) 1997-08-11 1997-08-11 Flammwidrige wärmeformbeständige Polycarbonat-ABS-Formmassen
DE19734663.4 1997-08-11

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WO1999007779A1 true WO1999007779A1 (fr) 1999-02-18

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US (1) US6566428B1 (fr)
EP (1) EP1003808B1 (fr)
JP (1) JP4257688B2 (fr)
KR (1) KR100554585B1 (fr)
CN (1) CN1153805C (fr)
AU (1) AU9156898A (fr)
BR (1) BR9811887A (fr)
CA (1) CA2300218C (fr)
DE (2) DE19734663A1 (fr)
DK (1) DK1003808T3 (fr)
ES (1) ES2175766T3 (fr)
HK (1) HK1030619A1 (fr)
TW (1) TW517071B (fr)
WO (1) WO1999007779A1 (fr)

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US6174942B1 (en) 1999-01-22 2001-01-16 General Electric Company Flame retardant polymer blends, and method for making
US6204313B1 (en) 1999-01-22 2001-03-20 General Electric Company Flame retardant polymer blends, and method for making
US6228912B1 (en) 1999-01-22 2001-05-08 General Electric Company Flame retardant resin compositions containing phosphoramides and method for making
US6388046B1 (en) 1998-08-31 2002-05-14 General Electric Company Flame retardant resin compositions containing phosphoramides, and method for making
US6433046B1 (en) 1999-01-22 2002-08-13 General Electric Company Flame retardant resin compositions containing phosphoramides, and method of making
US6569929B2 (en) 1999-01-22 2003-05-27 General Electric Company Method to prepare phosphoramides, and resin compositions containing them
US7019056B2 (en) 2001-01-09 2006-03-28 Bayer Aktiengesellschaft Flame retardants which contain phosphorus, and flame-retardant thermoplastic molding compositions
KR100611448B1 (ko) * 1999-12-30 2006-08-09 제일모직주식회사 폴리카보네이트/스티렌계 수지 조성물
USD621068S1 (en) 2002-03-01 2010-08-03 3Form, Inc. Architectural panel with thatch reed design
US8241714B2 (en) 2004-09-01 2012-08-14 3Form, Inc. Architectural panels with objects embedded in resin interlayer
USD691289S1 (en) 2012-09-05 2013-10-08 3Form, Inc. Panel with cut and aligned thatch interlayer
US9348065B2 (en) 2007-05-08 2016-05-24 3Form, Llc Multivariate color system with texture application
WO2021063630A1 (fr) * 2019-10-01 2021-04-08 Evonik Operations Gmbh Procédé de production de compositions thermoplastiques pour des composants soumis à des contraintes mécaniques et/ou thermiques

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DE10061078A1 (de) 2000-12-08 2002-06-13 Bayer Ag Flammwidrige wärmeformbeständige Polycarbonat-Zusammensetzungen
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KR100650910B1 (ko) * 2004-10-13 2006-11-27 제일모직주식회사 난연성 열가소성 수지 조성물
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KR100886348B1 (ko) * 2008-04-14 2009-03-03 제일모직주식회사 상용성이 개선된 난연 내스크래치 열가소성 수지 조성물
KR101188349B1 (ko) * 2008-12-17 2012-10-05 제일모직주식회사 투명성 및 내스크래치성이 향상된 폴리카보네이트계 수지 조성물
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WO2019206416A1 (fr) 2018-04-26 2019-10-31 Henkel Ag & Co. Kgaa Composé azoté quaternaire destiné à être utilisé en tant que catalyseur latent dans des compositions durcissables
CN115151608A (zh) 2020-01-02 2022-10-04 科思创有限公司 耐化学性聚碳酸酯共混组合物
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WO2000012609A1 (fr) * 1998-08-31 2000-03-09 General Electric Company Melanges de polymeres ignifugeants et leur procede de fabrication
KR100805574B1 (ko) * 1998-08-31 2008-02-20 제너럴 일렉트릭 캄파니 난연성 중합체 블렌드 및 그의 제조 방법
US6388046B1 (en) 1998-08-31 2002-05-14 General Electric Company Flame retardant resin compositions containing phosphoramides, and method for making
US6228912B1 (en) 1999-01-22 2001-05-08 General Electric Company Flame retardant resin compositions containing phosphoramides and method for making
US6204313B1 (en) 1999-01-22 2001-03-20 General Electric Company Flame retardant polymer blends, and method for making
US6433046B1 (en) 1999-01-22 2002-08-13 General Electric Company Flame retardant resin compositions containing phosphoramides, and method of making
US6569929B2 (en) 1999-01-22 2003-05-27 General Electric Company Method to prepare phosphoramides, and resin compositions containing them
US6174942B1 (en) 1999-01-22 2001-01-16 General Electric Company Flame retardant polymer blends, and method for making
KR100611448B1 (ko) * 1999-12-30 2006-08-09 제일모직주식회사 폴리카보네이트/스티렌계 수지 조성물
US7019056B2 (en) 2001-01-09 2006-03-28 Bayer Aktiengesellschaft Flame retardants which contain phosphorus, and flame-retardant thermoplastic molding compositions
USD621068S1 (en) 2002-03-01 2010-08-03 3Form, Inc. Architectural panel with thatch reed design
US8241714B2 (en) 2004-09-01 2012-08-14 3Form, Inc. Architectural panels with objects embedded in resin interlayer
US9348065B2 (en) 2007-05-08 2016-05-24 3Form, Llc Multivariate color system with texture application
USD691289S1 (en) 2012-09-05 2013-10-08 3Form, Inc. Panel with cut and aligned thatch interlayer
WO2021063630A1 (fr) * 2019-10-01 2021-04-08 Evonik Operations Gmbh Procédé de production de compositions thermoplastiques pour des composants soumis à des contraintes mécaniques et/ou thermiques

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DK1003808T3 (da) 2002-08-26
DE59804070D1 (de) 2002-06-13
JP2001512766A (ja) 2001-08-28
CN1266450A (zh) 2000-09-13
KR20010022768A (ko) 2001-03-26
AU9156898A (en) 1999-03-01
TW517071B (en) 2003-01-11
KR100554585B1 (ko) 2006-03-03
EP1003808A1 (fr) 2000-05-31
CA2300218C (fr) 2007-11-20
CA2300218A1 (fr) 1999-02-18
BR9811887A (pt) 2000-08-22
JP4257688B2 (ja) 2009-04-22
US6566428B1 (en) 2003-05-20
CN1153805C (zh) 2004-06-16
HK1030619A1 (en) 2001-05-11
EP1003808B1 (fr) 2002-05-08
DE19734663A1 (de) 1999-02-18
ES2175766T3 (es) 2002-11-16

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